Azo compounds and material colored therewith



Patented Oct. 14, 1941 UITED STATES t AZO. COMPOUNDS. AND COLORED 'THEREWITH v Joseph B. Dickey and MaxM. Levine, Rochester, N. Y., assignors'to Eastman- Kodak Company, Rochester; N. Y., a corporationsof'New Jersey No Drawing. Original application-April 27,; 1940,, Serial No. 332,040. Divided-and this. applica: 7 tion December 30, 1940, SerialNQ-372,358.

(01.: zed-20 s.)

4. Claims.

wherein R1 represents a member selected from the group consisting of fi-hydroxyethyl, monohydrcxypropyl and glyceryl constitute a very valuable class of dye compounds. The present application is a division of our copending application Serial No. 332,040, filed April 2'7, 1940.

The azo dye compounds of our invention have been found to be of particular value for the dyeing of organic derivatives of cellulose especially cellulose acetate silk and by means of them these materials, particularly textile material madeof cellulose acetate silk, can be dyed reddish-orange shades of very excellent fastness to light and washing. Further, the azo dye compounds of our invention possess excellent affinity for cellulose acetate silk and dye this material rapidly even at temperatures as low as 60-65" C. This advantage is of real importance, for example, in jig dyeing operations and results in lowered dyeing costs since less heat is required in the dyeing operation. Another advantage possessed by the dye compounds of our invention is that deep dyeings can be obtained with as little as 1% pure dye (by weight on the cloth). The dye compounds of our invention likewise find application for use in mixtures of dyes particularly in mixtures yielding brown and black dyeings.

Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters, such as cellulose acetate, cellulose formate, cellulose propionate or cellulose butyrate, and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose, such as cellulose acetate-propionate, cellulose acetate-butyrate, and the cellulose ethers, such as methyl cellulose, ethyl cellulose or benzyl cellulose. While the dye compounds of our invention will be described more particularly with reference to their application for the coloration of cellulose acetate silk, it will be understood that they can be employed for the coloration of organic derivatives of cellulose generally such as those just named.

The azodye compounds of our invention can coupling the diazonium compound obtained with a compound having the general formula:

wherein R; represents" s-hydroxyethyl,

hydroiwpropyl or glyceryl.

The. following examples illustrate the prep-aration of the azo dye compounds of our invention:

Eaample 1 13.8 grams of p-nitroaniline are diazotized in known fashion and the diazonium compound obtained is added slowly with stirring to a cold dilute hydrochloric acid solution of 17.1 grams of c-hydroxyethyl-o-toluidine. The coupling reaction which takes place is completed by the addition of sodium carbonate until the reaction mixture is neutral to Congo red paper. The dye compound formed is recovered by filtration, washed with water and dried. The dye compound obtained has the formula:

and colors cellulose acetate silk a reddish-orange shade.

Equivalent gram molecular weights of ,6- hydroxypropyl-o-toluidine and 'y-hydroxypropylo-toluidine can be substituted for the p-hydroxyethyl-o-toluidine of the example to obtain the dye compounds p-nitrobenzeneazo-,3-hydroxypropyl-o-toluidine and p-nitrobenzeneazo-y-hydroxypropyl-o-toluidine, respectively, which color cellulose acetate silk a reddish-orange shade.

Example 2 mono- 13.8 grams of p-nitroaniline are diazotized in known fashion and the diazonium compound obtained is coupled with an equivalent gram molecular weight of monoglyceryl-o-toluidine. Coupling and recovery of the dye compound formed can be carried out as described in Example 1. The dye compound obtained has the formula:

H rrmOrvmvQrr-cmononcmon and colors cellulose acetate silk a reddish-orange color.

The azo dye compounds of our invention are be prepared by diazotizing para nitroaniline and relatively insoluble in water. They may be employed for the direct dyeing of organic derivatives of cellulose particularly textile materials made of such materials by grinding to a fine powder, intimately mixing with a suitable dispersing or solubilizing agent and adding the resulting mixture to water or a dilute solution of soap and water to form an aqueous dyebath. Following this known preparation of the dyebath, the textile material, for example, to be dyed may be added to the dye- 5 formula:

bath and the dyeing operation conducted 0: wherein R represents a member selected from the known fashion. For a more complete description as to how the azo dye compounds of our invention may be employed in coloring operations; ref-- erence may be had to McNally andDickeytU. S.

Letters Patent No. 2,115,030, issued April 26, 1938, 1

wherein the coloration of organic derivatives of cellulose textile materials and. more particularly cellulose acetate silk textile materials is described. It will be understood, however, that with the dye compounds of the present invention colorations of excellent fastness to light and washing can be obtained with smaller concentrations of dye then specifically indicated in said Letters Patent. Again, the dyeing operation may be conducted at a somewhat lower temperature than that indicated, for example, a temperature of 60-65 C. although the temperature specifically set forth in said Letters Patent can be employed if desired. It will be understood that coloration group consisting of p-hydroxyethyl, monohydroxypropyl and glyceryl.

2. The azo dye'compound having the formula:

4. The: azo dye compound having the formula:

NOzON=NQN-CHzCHOHCHa CH:

JOSEPH B. DICKEY. MAX M. LEVINE. 

